Synthesis of hexacarboxylic acid linker based metal organic frameworks for applications in selective co2 capture and chemical fixation of co2

VIETNAM NATIONAL UNIVERSITY HCMC UNIVERSITY OF SCIENCE NGUYEN THI KIEU PHUONG SYNTHESIS OF HEXACARBOXYLIC ACID LINKERBASED METAL-ORGANIC FRAMEWORKS FOR APPLICATIONS IN SELECTIVE CO2 CAPTURE AND CHEMICAL FIXATION OF CO2 PhD THESIS in CHEMISTRY HOCHIMINH CITY – 2018 VIETNAM NATIONAL UNIVERSITY HCMC UNIVERSITY OF SCIENCE NGUYEN THI KIEU PHUONG SYNTHESIS OF HEXACARBOXYLIC ACID LINKERBASED METAL-ORGANIC FRAMEWORKS FOR APPLICATIONS IN SELECTIVE CO2 CAPTURE AND CHEMICAL FIXATION OF CO2 Major: Theoretical and Physical Chemistry Major Code: 62440119 Reviewer 1: Prof Dr Sc Luu Cam Loc Reviewer 2: Assoc Prof Dr Tran Ngoc Quyen Reviewer 3: Dr Pham Cao Thanh Tung Independent reviewer 1: Prof Dr Sc Luu Cam Loc Independent reviewer 2: Assoc Prof Dr Pham Thanh Huyen SUPERVISOR Assoc Prof Dr Ton That Quang Assoc Prof Dr Nguyen Thai Hoang HOCHIMINH CITY – 2018 TABLE OF CONTENTS LIST OF FIGURES LIST OF SCHEMES AND TABLES .13 LIST OF ABBREVIATIONS 15 ASSURANCE 16 ACKNOWLEDGMENTS .17 Abstract of the Dissertation .19 Chapter One 21 Introduction of Metal-Organic Frameworks for Applications in Selective CO2 Capture and Chemical Fixation of CO2 21 1.1 Introduction of Metal-Organic Framework (MOF) 21 1.1.1 Metal-Organic Framework (MOF) and Reticular Chemistry 21 1.1.2 Introduction of Hexacarboxylic-Acid-based Organic Building and Inorganic Building Units 26 1.2 Carbon Dioxide Capture and Separation 32 1.3 MOFs for Selective CO2 Capture 36 1.3.1 MOFs with Open Metal Sites 37 1.3.2 MOFs Functionalized by Nitrogen Bases 38 1.3.3 MOFs Controlled Pore Size .40 1.4 Introduction of CO2 Conversion for Fine Chemicals .41 1.4.1 Introduction of Cycloaddition of CO2 to Epoxides for Synthesis of Cyclic Carbonate 43 1.4.2 Mechanism of Cycloaddition of CO2 to Epoxides 45 1.4.3 One-pot Oxidative Carboxylation of Styrene and CO2 Forming Styrene Carbonate 49 1.5 MOF Materials as Heterogeneous Catalysts for the Cycloaddition of CO2 to Epoxides .51 1.5.1 MOFs with active Lewis acid metal sites .53 1.5.2 MOFs with Dual Catalytic Metal Centers 54 1.5.3 MOFs with Both Acid and Base Active Sites 56 1.6 Scope of the Dissertation 57 Chapter Two 59 Experimental .59 2.1 Materials and Analytical Techniques .59 2.1.1 Materials 59 2.1.2 Analytical Techniques 61 2.2 Synthesis of 1′,2′,3′,4′,5′,6′-hexakis(4-carboxyphenyl)-benzene (H6CPB) 63 2.3 Synthesis of MOF-888, MOF-889, MOF-890, MOF-892, and MOF-893 .65 2.3.1 Synthesis of MOF-888 .65 2.3.2 Synthesis of MOF-889 .65 2.3.3 Synthesis of MOF-890 .66 2.3.4 Synthesis of MOF-892 .67 2.3.5 Synthesis of MOF-893 .67 2.4 Gas Adsorption Properties 68 2.4.1 Determination of Surface Area 68 2.4.2 Determine Pore Size Distribution 69 2.4.3 Calculation of Gas Selectivity by Henry’s Law .70 2.4.4 Breakthrough Measurements 71 2.5 Catalysis Study on Chemical Fixation of CO2 to Cyclic Carbonate Synthesis .72 2.5.1 General Procedures 72 2.5.2 Catalytic Cycloaddition of CO2 to Epoxides 77 2.5.3 Methyl Esterification of MOF-892 78 2.5.4 Oxidative Carboxylation of CO2 and Styrene 79 2.5.5 Purification of Cyclic Carbonates 80 Chapter Three 81 Result and Discussion .81 3.1 Synthesis of a Series of Hexacarboxylic Acid Linker-Based Metal−Organic Frameworks and their Selective CO2 Capture .81 3.1.1 Overview 81 3.1.2 Synthesis of 1′,2′,3′,4′,5′,6′-hexakis(4-carboxyphenyl)-benzene (H6CPB) 83 3.1.3 Crystal Structures of MOF-888, -889, and -890 85 3.1.4 Characterization of MOF-888, -889, and -890 .93 3.1.5 Gas Adsorption Properties .100 3.2 Synthesis of Zirconium-Based Metal−Organic Frameworks as Reusable Catalysts for Chemical Fixation of CO2 108 3.2.1 Overview 108 3.2.2 Crystal Structures of MOF-892 and MOF-893 110 3.2.3 Characterization of MOF-892 and MOF-893 115 3.2.4 Catalytic Cycloaddition of CO2 to Epoxides and Olefins 123 Conclusion and Outlook 147 Conclusion 147 Outlook 148 New MOFs for Gas Separation 148 New MOF-based Catalysts for Chemical Fixation of CO2 149 PUBLICATIONS 150 REFERENCES 151 APPENDIX .169 Appendix A: Synthesis of a Series of Hexacarboxylic Acid Linker-Based Metal−Organic Frameworks and their Selective CO2 Capture .170 Appendix B: Synthesis of Zirconium-Based Metal−Organic Frameworks as Reusable Catalysts for Chemical Fixation of CO2 183 LIST OF FIGURES Figure 1.1 Metal-containing clusters and their corresponding SBUs Atom colors: metal, blue polyhedra; C, black; O, red 22 Figure 1.2 Rods with points of extension forming (A) zigzag ladder,5 (B) infinite,6 (C) twisted ladder.5 Atom colors: metal, blue polyhedra; C, black; O, red 22 Figure 1.3 Organic linkers (top) and their corresponding SBUs (bottom) Atom colors: C, black; O, red 23 Figure 1.4 (A) MOF-5 showing the abstraction of the Zn4O(−CO2)6 SBU as an octahedron, the ditopic terephthalate linker as a linear rod, and their assembly into the pcu net shown in augmented form (B) HKUST-1 showing the Cu2(−CO2)4 paddle wheel abstracted as a square, the tritopic linker as a triangle, and their combination to form the tbo net shown in augmented form tbo-a Atom colors: Zn (for MOF-5) and Cu (for HKUST-1), blue polyhedra; C, black; O, red; all H atoms are omitted for clarity The large yellow, orange and pink spheres represent the largest sphere that would occupy the cavity All hydrogen atoms are omitted for clarity 24 Figure 1.5 Representative binodal nets in reticular chemistry.9 25 Figure 1.6 The isoreticular (maintaining same topology) expansion of archetypical MOFs resulting from discrete inorganic SBUs combined with ditopic organic linkers to obtain MOFs in a pcu net Atom colors: Zn, blue polyhedra; C, black; O, red The yellow spheres are placed in the structure to indicate space in the cage 26 Figure 1.7 Topologies and shapes for hexatopic linkers: (a−c) trigonal prisms, (d, e) octahedra, and (f-g) hexagon 27 Figure 1.8 Schematic of the crystal structure of a NU-111, -100, and -110 from left to right, respectively Color code: Cu, blue; C, black; O, red All H atoms are omitted for clarity The yellow and orange spheres are placed in the structure to indicate space in the cage 28 Figure 1.9 Crystal structure of NU-110E Hexacarboxylic linker (H6L) connects to a Zr6 SBU forming the three-dimensional structure adopting she topology Color code: Cu, blue; C, black; O, red All H atoms are omitted for clarity The yellow and orange spheres are placed in the structure to indicate space in the cage 28 Figure 1.10 Hexaarylbenzene based-covalent organic framework 30 Figure 1.11 Inorganic SBUs of various coordination numbers are known in the family of the zirconium-based MOFs Atom colors: Zr, blue polyhedra; C, black; O, red All H atoms are omitted for clarity 31 Figure 1.12 Representative binodal nets in reticular chemistry adopted in zirconium MOFs 32 Figure 1.13 (A) Atmospheric CO2 concentration (at Mauna Loa Observatory), showing the continuing and increase of CO2 in atmosphere during 1958–2017 (B) Atmospheric concentrations of the greenhouse gases carbon dioxide (CO2, green), methane (CH4, orange) and nitrous oxide (N2O, red) determined from ice core data (dots) and from direct atmospheric measurements (lines) 33 Figure 1.14 Three main types of CO2 capture in the current technology 34 Figure 1.15 Crystal structure of M-MOF-74 DOT link is joined by an infinite metal oxide SBU to make the three-dimensional structure with one-dimensional hexagonal channels and adopting the etb topology Atom colors: metal, blue polyhedra; C, black; O, red All H atoms are omitted for clarity 38 Figure 1.16 Crystal structure of bio-MOF-11 Co2+-adeninate-acetate clusters (A) are bridged by adeninate to generate an extended 3D porous structure (B) The framework adopts the augmented lvt topology (C) (D) CO2 (circles) and N2 (triangles) isotherms at 273 (black) and 298 K (red) (C) Isosteric heat of adsorption of CO2 Atom colors: Co, blue polyhedra; C, black; O, red All H atoms are omitted for clarity 39 Figure 1.17 Crystal structure of Mg(dobpdc)2-dmpn and structure of Mg2(dobpdc)− (dmpn−CO2) after activation of Mg(dobpdc)2-dmpn and dosing with bar of CO2, forms bridging carbamic acid pairs Atom colors: Mg, blue polyhedra; C, black; O, red All H atoms are omitted for clarity 40 Figure 1.18 Crystal structure of PCN-200 and gas adsorption isotherms for CO2 and N2 of PCN-200 Atom colors: Cu, blue polyhedra; C, black; O, red All H atoms are omitted for clarity 41 Figure 1.19 The possible applications of CO2 in chemical syntheses 42 Figure 1.20 Common co-catalysts used in the reaction of CO2 and epoxides 48 Figure 1.21 Most probable sites of nucleophilic attack for different epoxides 49 Figure 1.22 Hf-NU-1000 shows high catalytic activity for the activation of epoxides leading to the regioselective and enantio-retentive formation of 1,2-bifuctionalized systems Atom colors: Hf, blue; C, black; O, red, all H atoms are omitted for clarity 53 Figure 1.23 Crystal structure of MMCF-2 Tetracarboxylic linker, H4LCu2, connects to a paddle-wheel copper cluster forming the three-dimensional structure adopting nbo topology Atom colors: Cu, blue polyhedra; C, black; O, red; N, light blue; all H atoms are omitted for clarity 54 Figure 1.24 Crystal structure of PCN-224(Co) Tetracarboxylic linker (H4L) connects to a Zr6 SBU forming the three-dimensional structure adopting she topology Atom colors: Zr, blue polyhedra; C, black; O, red; N, light blue; Co, pink; all H atoms are omitted for clarity 55 Figure 1.25 Synthesis of Im-UiO-66 and (I-)Meim-UiO-66 via solvothermal reaction and by post-synthetic modification method, respectively Atom colors: Zr, green polyhedra; C, black; O, red; N, blue All H atoms are omitted for clarity 56 Figure 1.26 The route to synthetic route in the preparation of catalyst MIL-101-N(n-Bu)3Br and MIL-101-P(n-Bu)3Br (R = N or P) 57 Figure 2.1 Apparatus used for collection of breakthrough curves 71 Figure 2.2 Calibration curve of styrene oxide (SO, top) and styrene carbonate (SC, bottom) to determine the conversion, selectivity and GC yield of the cycloaddition reaction 74 Figure 2.3 Calibration curve of propylene oxide (PO, top) and propylene carbonate (PC, bottom) to determine the conversion, selectivity and GC yield of the cycloaddition reaction 75 Figure 2.4 Calibration curve of cyclohexene oxide (CO, top) and cyclohexene carbonate (CC, bottom) to determine the conversion, selectivity and GC yield of the cycloaddition reaction 76 Figure 2.5 Calibration curve of styrene to determine the conversion, selectivity and GC yield of the one-pot reaction 77 Figure 3.1 ORTEP representation of the asymmetric unit of MOF-888 displayed with 50% probability The site occupancy factors of Ni atoms are 0.5 Atom colors: Ni, violet; O, red; H, white; and C, grey 87 Figure 3.2 Crystal structure of MOF-888 (A) Linking of hexagonal CPB and triangular Ni(CO2)3 SBUs result in (B) MOF-888 (C) The structure of MOF-888 adopts the kgd topology Atom colors: Ni, blue polyhedra; C, black, O, red, all H atoms are omitted for clarity 88 Figure 3.3 ORTEP representation of the asymmetric unit of MOF-889 displayed with 50% probability The site occupancy factors of the disordered fragments for DEF and EtOH are 0.5 each Except for the C atoms in one EtOH (O16-C58-C59), the other EtOH C atoms were refined isotropically The N and C atoms in the disordered DEF were also treated isotropically due to their abnormal anisotropic thermal parameters Atom colors: Mg, turquoise; O, red; H, white; N, blue; and C, grey 89 Figure 3.4 Crystal structure of MOF-889 (A) Linking of hexagonal CPB and infinite [Mg2(CO2)4(CO2H)2(EtOH)2]∞ (red and blue binodal rod) SBUs result in (B) MOF-889 (C) The structure of MOF-889 adopts the yav topology Atom colors: Mg, blue polyhedra; C, black, O, red, all H atoms, except for those participating in hydrogen bonding, are omitted for clarity 90 Figure 3.5 ORTEP representation of the asymmetric unit of MOF-890 displayed with 50% probability Besides Cu and O1w atoms, all non-H atoms were treated isotropically due to their abnormal anisotropic thermal parameters Atom colors: Cu, violet; O, red; C, grey; H, white; and N, blue 91 Figure 3.6 Crystal structure of MOF-890 (A) Linking of hexagonal CPB and trigonal prismatic Cu3(CO2)6 SBUs result in (B) MOF-890 (C) The structure of MOF-890 adopts the novel htp topology Atom colors: Cu, blue polyhedra; C, black, O, red, all H atoms are omitted for clarity 92 Figure 3.7 Comparison of simulated (black) PXRD pattern from the crystal data with those of the experimental as-synthesized (red) and activated (blue) of MOF-888 93 Figure 3.8 Comparison of simulated (black) PXRD pattern from the crystal data with those of the experimental as-synthesized (red) and activated (blue) of MOF-889 94 Appendix B7 Characterizations of cyclic carbonates Styrene carbonate Propylene carbonate Cyclohexene carbonate H NMR (500 MHz) DMSO-d6, δ (ppm) = 7.42–7.48 (m, 5H), 5.85 (t, 1H, J = 7.5, 8.0 Hz), 4.87 (t, 1H, J = 8.0, 8.5 Hz), 4.40 (t, 1H, J = 8.0, 8.5 Hz) CDCl3, δ (ppm) = 4.82−4.75 (m, 1H), 4.48 (t, J = 8.0, 8.5 Hz, 1H), 3.94 (t, J = 7.0 Hz, 1H), 1.39 (d, J = 6.0 Hz, 1H) CDCl3, δ (ppm) = 4.67 – 4.63 (m, 2H), 1.90 – 1.80 (m, 4H), 1.61 – 1.53 (m, 2H), 1.42 – 1.35 (m, 2H) 13 C NMR (125 MHz) CDCl3, δ (ppm) = 155.2, 136.8, 129.8, 129.4, 127.1, 78.2, 71.3 CDCl3, δ (ppm) = 155.1, 73.7, 70.7, 19.3 CDCl3, δ (ppm) = 155.2, 73.7, 70.7, 19.2 GC-MS (EI, 70 eV) m/z: 164 ([M]+), 119, 105, 90 m/z: 102 ([M]+), 87, 57, 43, 29, 15 m/z: 142 ([M]+), 97, 83, 69, 55, 41, 27, 17 ṽ (cm-1) = 2989, 1781, 1558, 1485, 1456, 1388, 1353, 1173, 1117, 1043, 955, 848, 774, 710 ṽ (cm-1) = 2943, 2868, 1782, 1559, 1452, 1434, 1352, 1308, 1207, 1165, 1138, 1026, 995, 953, 905, 857, 820, 780, 730 FT-IR ṽ (cm-1) = 2981, 2924, (KBr, 4000 1778, 1549, 1492, – 400 cm-1) 1456, 1393, 1359, 1328, 1286, 1175, 1058, 958, 903, 830, 757, 696, 609, 554, 490 186 Appendix B8 1H (top) and 13C (bottom) NMR spectra of styrene carbonate 187 Appendix B9 1H (top) and 13C (bottom) NMR spectra of propylene carbonate 188 Appendix B10 1H (top) and 13C (bottom) NMR spectra of cyclohexene carbonate 189 Appendix B11 FT-IR of styrene carbonate 190 Appendix B12 FT-IR of propylene carbonate 191 Appendix B13 FT-IR of cyclohexene carbonate 192 Appendix B14 GC-MS spectra of styrene carbonate 193 Appendix B15 GC-MS spectra of propylene carbonate 194 Appendix B16 GC-MS spectra of cyclohexene carbonate 195 Appendix B17 Crystal data and structure refinement for MOF-892 Compound Empirical formula Formula weight Temperature/K Crystal system Space group a/Å b/Å c/Å α/° β/° γ/° Volume/Å3 Z ρcalcg/cm3 μ/mm-1 F(000) Crystal size/mm3 Radiation 2θ range for data collection/° Index ranges Reflections collected Independent reflections Data/restraints/parameters Goodness-of-fit on F2 Final R indexes [I >= 2σ(I)] Final R indexes [all data] Largest diff peak/hole / e Å-3 MOF-892 C56.67H24NO28.67Zr4 1542.31 100 hexagonal P63/m 32.2282(14) 32.2282(14) 26.5480(12) 90 90 120 23880(2) 0.643 0.289 4562.0 0.14 × 0.09 × 0.08 MoKα (λ = 0.71073) 4.154 to 39.766 -30 ≤ h ≤ 30, -30 ≤ k ≤ 30, -25 ≤ l ≤ 25 93928 7507 [Rint = 0.0722, Rsigma = 0.0376] 7507/90/365 2.247 R1 = 0.1554, wR2 = 0.4612 R1 = 0.1775, wR2 = 0.4922 1.99/-1.23 R1 = ∑||Fo| ̶ |Fc||/∑|Fo|, wR2 = [∑w(Fo2 – Fc2)2/w(Fo)2]1/2 196 Appendix B18 Crystal data and structure refinement for MOF-893 Compound Empirical formula Formula weight Temperature/K Crystal system Space group a/Å b/Å c/Å α/° β/° γ/° Volume/Å3 Z ρcalcg/cm3 μ/mm-1 F(000) Crystal size/mm3 Radiation 2θ range for data collection/° Index ranges Reflections collected Independent reflections Data/restraints/parameters Goodness-of-fit on F2 Final R indexes [I>=2σ (I)] Final R indexes [all data] Largest diff peak/hole / e Å-3 MOF-893 C102H48O44Zr6 2524.72 100.0 monoclinic C2/c 24.6147(9) 69.169(2) 19.5485(7) 90 92.081(2) 90 33261(2) 1.008 0.420 10016.0 0.08 × 0.048 × 0.022 MoKα (λ = 0.71073) 3.938 to 41.732 -24 ≤ h ≤ 24, -69 ≤ k ≤ 69, -19 ≤ l ≤ 19 140110 17503 [Rint = 0.1080, Rsigma = 0.0519] 17503/41/1206 1.037 R1 = 0.0725, wR2 = 0.1942 R1 = 0.0976, wR2 = 0.2158 1.26/-0.75 R1 = ∑||Fo| ̶ |Fc||/∑|Fo|, wR2 = [∑w(Fo2 – Fc2)2/w(Fo)2]1/2 197 Appendix B19 Comparison of as-synthesized (black), activated (red) PXRD pattern of MOF-892 with the MOF-892 collected after suspension in water (blue) PXRD pattern Appendix B20 Comparison of as-synthesized (black), activated (red) PXRD pattern of MOF-893 with the MOF-893 collected after suspension in water (blue) PXRD pattern 198 Appendix B21 CO2 isotherms for comparative MOFs at 298 K Filled and open symbols represent adsorption and desorption branches, respectively The connecting curves are guides for the eye Appendix B22 Optical microscope image of single crystal MOF-892 after esterification 199 Appendix B23 N2 isotherms of MOF-892 (red), and esterified MOF-892 (Me-MOF892) (blue) at 77 K Filled and open symbols represent adsorption and desorption branches, respectively The connecting curves are guides for the eye Appendix B14 CO2 isotherms of MOF-892 (red) and esterified MOF-892 (MeMOF-892) (blue) at 273 K Filled and open symbols represent adsorption and desorption branches, respectively The connecting curves are guides for the eye 200 ... UNIVERSITY OF SCIENCE NGUYEN THI KIEU PHUONG SYNTHESIS OF HEXACARBOXYLIC ACID LINKERBASED METAL- ORGANIC FRAMEWORKS FOR APPLICATIONS IN SELECTIVE CO2 CAPTURE AND CHEMICAL FIXATION OF CO2 Major:... 21 Introduction of Metal- Organic Frameworks for Applications in Selective CO2 Capture and Chemical Fixation of CO2 21 1.1 Introduction of Metal- Organic Framework (MOF) 21 1.1.1 Metal- Organic. .. that my work in this dissertation, entitled ? ?Synthesis of Hexacarboxylic Acid Linker based Metal- Organic Frameworks for Applications in Selective CO2 Capture and Chemical Fixation of CO2? ?? is assured